Process of producing alloys and the separation of metals.



P. F. GOWING. PROCESS OF PRODUCING ALLOYS AND THE SEPARATION OF METALS.

APPLICATION FILED NOV. 11, 1909.

969,773. Patented Sept 13, 1910.

\Nilnesses; Inventor, g z g g1 Percy Foolhe' owing,

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Alfornqy PERCY FOOTE CO'WING, OF NEW YORK, N. Y.

PROCESS OF PRODUCING ALLOYS AND THE SEPARATION OF METALS.

Specification of Letters Patent.

Patented Sept. 13, 1910.

Application filed November 11, 1909. Serial No. 527,407.

To all whom it may concern:

Be it known that I, PERCY Foo'rE Gowmo,

' a citizen of the United States of America,

and a resident of the city of New York, county of New York, and State of New York, have invented certain new and use ful Improvements in Processes for Producing Alloys and the Separation of Metals, of which thefollowing isa specification.

My invention is a metallurgical process and relates to the electrolytic treatment of alloys containing principally copper and nickel, and in certain cases iron, the object being to separate the copper and torecover nickeland iron economically and by simple operations. The nickel and iron are obtained in the form of a compact thick deposit on the cathode.

In carrying out my process the original alloy is placed as an anode in an electrolytic bath, which, upon the passage of the current has the property of dissolving substantially all of the metals of the ori inal alloy. That portion of the electrolyte orming the resultant solution is thentreated in such manner as to replace the copper by iron, or

nickel and iron, and nickel and iron are thereafter electrolytically deposited.

Though I do not limit myself to the use thereof, I have found that a warm, rather concentrated substantially neutral aqueous solution of nickel chlorid is a suitable initial electrolyte for carrying out the process. The very soluble nickel chlorid dissolved in water as described forms, especially when hot, an electrolyte of low electrical resistance and permits the use of high current densities. If the precautions herein pointed out are observed, such an electrolyte adjusts itself during the operation of the process to the particular original alloy under treatment, as will be readily understood.

Well known instrumentalities can be employed in performing my process, and for the urposes of illustration, I have shown one lbrm of apparatus by which the process can be worked, but without intending to be confined thereto.

In the accompanying sheet of drawings, which forms a part of this application, the

figure is a cross-section through the several instrumentalities constituting the system.

Thefirst vat A comprises an anode compartment and a cathode compartment,

wherein the copper bearing alloy 1 to be treated is dissolved as the anode, and nickel and iron are deposited on the cathode. The

anode and cathode compartments are separated by adiaphragm 2. The rest of the apparatus is for modifying the copper-containing solution which is withdrawn from the anode compartment of this vat A and for discharging it, after proper treatment for the removal of the copper therefrom, into the cathode compartment thereof. The anode and cathode and the electrolytes in the two compartments of this vat constitute a divided electrolytic cell in which the alloy to be treated is dissolved and the desired metal or metals obtained. The dividing diaphragm of the vat is of that type which is sufliciently non-porous to prevent the mixing of the solutions on either side thereof to any appreciable degree, but at the same time has su cient porosity to allow the electric current to be conducted therethrough by the electrolyte in its pores without too greatl increasing the resistance. The original aloy is connected as the anode to a. positive bus-bar 3. \Vhen the electric current is passing, the original alloy goes into solution in the electrolyte in the anode compartment of the vat A. The solution thus formed is carried from the bottom of this compartment through a conduit 4: into a second electrolytic vat B in which selective deposition is carried on. this vat is composed of nickel or iron or both, and the cathode 6 may be composed of copper; but this is not essential. The electro yte is preferably a 'tated by stirrers 7 and may be heated. sufficiently low impressed voltage between the anode and cathode, the copper-containing solution from the anode compartment of the first vat A in its passa e through the second vat B is caused to deposit copper selectively upon the cathode 6, an equivalent amount of theanode 5 going into solution to replace the copper. It is not expected that all of the co per in the solution be so replaced. It is o vious that a series of vats for selective deposition of copper may be used. The solution is withdrawn from the vat for selective deposition, or from the last of these vats if more than one is used, through a conduit 8 which communicates with the interior of a receptacle or series of receptacles C wherein the copper still remaining in solution is removed The anode 5 in.

by cementation on iron. It is here shown as a tumbling barrel mounted on an In: clined axis by means of hollow trunnions 9 and 10, the conduit entering through the upper trunnion. This tumbling barrel contains loose ieces or fragmentsbf iron 11 which it is esired to substitute for the copper remainingin solution after leavlng the selective deposition vat. While the substitution is herein being effected by cementation, the tumbling action isof advantage as it dislodges some of the cemented copper v these if more than one is used, through the lower trunnion into a settlin tank D, in which any undissolved materia carried over mechanically is allowed to settle. The solution now freed from the salts of copper,

and containing the salts of iron, or iron and nickel, substituted therefor, is conveyed from the settling tank to a heatin tank E through a condult 12 by any suitab e means, a pump 13 being illustrated. A filter 14 can be introduced between the settling tank and the heating tank, if desired. This solution is then conveyed through a conduit 15 from the heating tank to the cathode compartment of the first vat A, the temperature of the solution being raised to a suflicient degree in the heating tank or in the vat A to main tainin the cathode compartment that temperature of the electrolyte at which the predetermine electrolytic process is most efiiciently carried on.' The bath in this cathode compartment contains nickel and iron in solution, A cathode 16 is immersed therein upon which metals are deposited from the solution. This cathode is suspended from a negative bus-bar 17. When the desired amount of metal has been deposited upon the cathode, the cathode is removed. The solution in the cathode compartment is allowed to flow over the dia hragm 2 into the anode compartment, therc circuit of flow. If desire the electro ytes in the anode and cathodecompartments of completin the Vat A ma be agitated by any'well known means. he deposit, or the cathode and deposit, constitute the product which my process is desi ned to secure. By depositing weights of nickel,:or nickel and iron, upon a cathode of known weight and material, as iron, the relative weights entation receptacle where the copper in solu-,

tion is replaced by iron.-

Throughout the process the 1ron and copper salts are formed and should be mamiained as far as possible in their reduced condition as ferrous and cuprous salts. Th1s is very advantageous as the copper 1s then in the best condition forcementation, requiring the smallest amount of iron for its replacement, and the iron is in the best condition forelectro-deposition. As no 1nsoluble anodes are used, the electrolyte remains at all times electro-chemically bal anced.- By this I mean, that whenever a metal is removed, either by electro-deposition or cementation, an equivalent ofsome metal or metals goes into 'solution in its place; hence no energy is wasted in gas generation, nor is the substantially neutral con- .dition of the electrolyte disturbed. Therefore as the electrolyte is not destroyed and adjusts itself to difi'erent original alloys, the process can be carried on indefinitely by merely supplying fresh anodes and cathodes,

and 1ron for cementation. When using the chlorid electrolyte referred to, the solution withdrawn from the anode compartment of the vat A is or becomes a mixture of nickel chlorid, ferrous chlorid and cuprous chlorid, and after the replacement of the. copper, it

becomes a solution of nickel and ferrous chlorids. It is also desirable in using this electrolyte that the anode used should contain as small a percentage of sulfur as is practicable, to keep down the formation of sulfates, andthese, if formed, may be removed by the occasional addition to the solution of barium chlorid or equivalent reagent. Should cobalt be present with the nickel it will react in the same manner in each of the processes herein set' forth, and whenever nickel is referred to, it is to be understood to include nickel and cobalt in combination. Frequently the anode mud, formed of constituents insoluble in the electrolyte, exhibits sufiicient cohesiveness to be removed with the nearly dissolved anode. It should not be permitted to remain intact on the anode beyond a certain thickness as the impurities may become an insoluble anode which would disturb the electrolyte balance of the solu-' tion, as chlorin instead of attacking the metal constituents of the anode would ap-- pear as free chlorin and oxidize the salts in solution, which it has been pointed out should be maintained in their reduced condition. Someof the mud may settle in the bottom of the anode compartment, and some may remain in suspension in the electrolyte from which it will be reinoved by the filters. Suitable filters, settling tanks, or heaters may be introduced in or between any of the vats or receptacles.

It may be found necessary in carrying out my process in some instances to introduce into the electrolytes a small amount of organic compounds, weakly dissociated acids, or salts, to improve the quality of the cathode deposit or to increase the conductivity of the electrolyte; also to add small amounts of free acids to prevent the formation of basic salts or to redissolye them if formed. But in making these additions of acids care should be taken to so limit them as to maintain the electrolyte in asubstantially neutral condition. It is not necessary that the metals of the so-called alloys be present therein in an alloyed state, as they might be mixtures, and when I refer to alloys in the claims, I mean to include metals chemically or mechanically combined.

Any suitable form of cathode can be employed in the first vat A for receiving the deposit of nickel and iron, but I have discovered that if the initial deposit is made upon a cathode so constituted as to hold it intact mechanically, for example, a cathode of wire mesh, gauze or netting, the deposit, which, if obtained by present methods shows a strong tendency to strip or peel oti', can be carried to considerable thickness without stripping, as the stripping takes place between the deposit and the ori inal cathode and not between the particles 0? layers of the deposited metal.

Vhat I claim as new, and desire to secure by Letters Patent of the United States, is-- 1. The process of eliminating copper t'rom alloys containing nickel and cop )er which consists in bringing the original alloy into solution electrolytically, substituting iron for copper in this solution, and electrolytically depositing nickel and iron from the solution thus obtained. substantially as described.

2. The process of eliminating copper from alloys containing nickel and co )per which consists in bringing the origina alloy into solution electrolytically, substituting nickel and iron for co )per in this solution. and electrolytically. tepositing nickel and iron from the solution thus obtained, substantially as described.

3. The process of eliminatingcopper from alloys containing nickel and co )Iper which consists in bringing the original a oy into solution electrolytically so that the copper is in a cuprous state and any iron present is in a ferrous state, substituting iron for copper in this solution and electrolytically depositing nickel and iron from the solution thus obtained, substantially as described.

4. The process of eliminating copper from alloys containing nickel and co per, which consists in bringing the origina alloy into solution electrolytically, so that the copper is in a cuprous state. substituting iron for copper in this solution so that the iron salts are in a ferrous state. and electrolytically depositing nickel and iron from the solution thus obtained, substantially as described.

5. The process of eliminating copper from alloys containing nickel and copper which consists in bringing the original alloy into solution electrolytically so that the copper is in a cuprous state and any iron present is in a ferrous state. substituting nickel and iron for copper in this solution. and electrolytically depositing nickel and iron from the solution thus obtained. substantially as described.

ti. The process of eliminating copper from alloys containing nickel and copper which" consists in bringing the orwina alloy into solution electrolytically. siibstituting iron for copper in this solution by cementation. and electrolytimilly depositing nickel and iron from the solution thus obtained, substantially as described.

7. The process of eliminating copper from alloys containing nickel and co mm which consists in bringing the original alloy into solution clcctrolytically. substituting iron for copper in this solution by selective dcposition and cementation, and electrolytically depositing nickel and iron from the solution thus obtained, substantially as described.

8. The process of eliminating copper from alloys containing nickel and on per which consists in bringing the original alloy into solution eleetrolyically, substituting nickel and iron for copper in this solution by selective deposition and cementation. and electrolytically depositing nickel and iron from the solution thus obtained, substantially as described.

9. The process of eliminating copper from alloys containing nickel and copper, which consists in connecting the alloy as the anode in an electrolyte comprising a concentrated substantially neutral aqueous solution of nickel and ferrous chlorids, withdrawing the solution thus formed. substituting iron for copper so that the iron shall be present in a ferrous condit' m. and electrolytically depositing nickel and iron from the solution thus obtained. substantiallv as described.

Signed by me at New 'ork, N. Y., this 10th day of November. 1909.

y PERCY FOOTE COWING.

\Vitnesses FRANK C. Conn. Santa-1i. W. Bacon. 

